Abstract We report the synthesis of ordered mesoporous ceria ( m CeO 2 ) with highly crystallinity and thermal stability using hybrid polymer templates consisting of organosilanes. Those organosilane-containing polymers can convert into silica-like nanostructures that further serve as thermally stable and mechanically strong templates to prevent the collapse of mesoporous frameworks during thermal-induced crystallization. Using a simple evaporation-induced self-assembly process, control of the interaction between templates and metal precursors allows the co-self-assembly of polymer micelles and Ce 3+ ions to form uniform porous structures. The porosity is well-retained after calcination up to 900 °C. After the thermal engineering at 700 °C for 12 h ( m CeO 2 -700-12 h), m CeO 2 still has a specific surface area of 96 m 2 g −1 with a pore size of 14 nm. m CeO 2 is demonstrated to be active for electrochemical oxidation of sulfite. m CeO 2 -700-12 h with a perfect balance of crystallinity and porosity shows the fastest intrinsic activity that is about 84 times more active than bulk CeO 2 and 5 times more active than m CeO 2 that has a lower crystallinity.
more »
« less
Thermal air oxidation changes surface and adsorptive properties of black carbon (char/biochar)
In this study, we systematically investigated the effects of thermal air oxidation on the properties of biomass-derived BC made at carbonization temperatures (HTTs) of 300–700 ˚C. BC produced by including air in the carbonization step was found to have a low surface area and underdeveloped pore structure. Substantial changes of BC were observed after post-pyrolysis thermal air oxidation (PPAO). Well-carbonized BC samples made anoxically at relatively high HTTs (600 and 700 ˚C) showed, after PPAO, significant increases in N2 BET surface area (SA) (up to 700 times), porosity (< 60 Å) (up to 95 times), and adsorptivity (up to 120 times) of neutral organic species including two triazine herbicides and one natural estrogen. Partially carbonized BC made at a lower HTT (300 or 400 ˚C) showed moderate increases in these properties after PPAO, but a large increase in the intensity of Fourier transform infrared spectroscopy bands corresponding to various oxygen-containing functional groups. Well-carbonized BC samples, on the other hand, were deficient in surface oxygen functionality even after the PPAO treatment. Adsorption of the test organic compounds on BC generally trended with BET SA when it was less than 300 m2/g, but BET SA was poorly predictive of adsorption when it was greater than 300 m2/g. Overall, our results suggest that thermal reactions between molecular oxygen and BC 1) increase surface oxygen functionality more effectively for low-HTT than for high-HTT BC samples; 2) increase SA and porosity (< 60 Å) especially for high-HTT BC samples; and 3) create new adsorption sites and/or relieve steric restriction of organic molecules to micropores, thereby enhancing the adsorptivity of BC. These results will prove useful not only for understanding the fate of environmental BC but also in devising strategies for improving the practical performance of the engineered form of BC (i.e., biochar).
more »
« less
- Award ID(s):
- 1709532
- PAR ID:
- 10074157
- Date Published:
- Journal Name:
- Science of the total environment
- Volume:
- 618
- ISSN:
- 0048-9697
- Page Range / eLocation ID:
- 276-283
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
A novel composite hydrogel bead composed of sodium alginate (SA) and aldehyde cellulose nanocrystal (DCNC) was developed for antibiotic remediation through a one-step cross-linking process in a calcium chloride bath. Structural and physical properties of the hydrogel bead, with varying composition ratios, were analyzed using techniques such as BET analysis, SEM imaging, tensile testing, and rheology measurement. The optimal composition ratio was found to be 40% (SA) and 60% (DCNC) by weight. The performance of the SA–DCNC hydrogel bead for antibiotic remediation was evaluated using doxycycline (DOXY) and three other tetracyclines in both single- and multidrug systems, yielding a maximum adsorption capacity of 421.5 mg g−1 at pH 7 and 649.9 mg g−1 at pH 11 for DOXY. The adsorption mechanisms were investigated through adsorption studies focusing on the effects of contact time, pH, concentration, and competitive contaminants, along with X-ray photoelectron spectroscopy analysis of samples. The adsorption of DOXY was confirmed to be the synergetic effects of chemical reaction, electrostatic interaction, hydrogen bonding, and pore diffusion/surface deposition. The SA–DCNC composite hydrogel demonstrated high reusability, with more than 80% of its adsorption efficiency remaining after five cycles of the adsorption–desorption test. The SA–DCNC composite hydrogel bead could be a promising biomaterial for future antibiotic remediation applications in both pilot and industrial scales because of its high adsorption efficiency and ease of recycling.more » « less
-
The novel material, one-dimensional lepidocrocite (1DL) titanate, is attracting industrial and scientific interest because of its applicability to a wide range of practical applications and its ease of synthesis and scale up of production. In this study, we investigated the CO2 adsorption capability and pore structures of 1DL freeze-dried and lithium chloride washed air-dried powders. The synthesized 1DL was characterized by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Using the constant-volume method, CO2 gas adsorption revealed that the 1DL exhibits type IV adsorption–desorption isotherms. The heats of adsorption obtained from the adsorption branches are lower than those obtained from the desorption branches. Brunauer–Emmett–Teller (BET) analysis, using N2 gas adsorption isotherms at 77 K showed that 1DL possesses 80.2 m2/g of BET specific surface area. Nonlocal density functional theory analysis indicated that two types of pores, meso-pores and ultramicro pores, exist in the 1DL freeze-dried powders. This work provides deep insights into the pore structures and CO2 adsorption mechanisms of 1DL powders.more » « less
-
Carbon dots (CDots) are classically defined as small carbon nanoparticles with effective surface passivation, which, in the classical synthesis, has been accomplished by surface organic functionalization. CDot-like nanostructures could also be produced by the thermal carbonization processing of selected organic precursors, in which the non-molecular nanocarbons resulting from the carbonization are embedded in the remaining organic species, which may provide the passivation function for the nanocarbons. In this work, a mixture of oligomeric polyethylenimine and citric acid in the solid state was used for efficient thermal carbonization processing with microwave irradiation under various conditions to produce dot samples with different nanocarbon content. The samples were characterized in terms of their structural and morphological features regarding their similarity or equivalency to those of the classical CDots, along with their significant divergences. Also evaluated were their optical spectroscopic properties and their photoinduced antimicrobial activity against selected bacterial species. The advantages and disadvantages of the thermal carbonization processing method and the resulting dot samples with various features and properties mimicking those of classically synthesized CDots are discussed.more » « less
-
Carbon dots (CDots) are generally defined as small carbon nanoparticles (CNPs) with effective surface passivation, for which the classical synthesis is the functionalization of pre-existing CNPs with organic molecules. However, “dot” samples produced by “one-pot” thermal carbonization of organic precursors are also popular in the literature. These carbonization-produced samples may contain nano-carbon domains embedded in organic matters from the precursors that survived the thermal processing, which may be considered and denoted as “nano-carbon/organic hybrids”. Recent experimental evidence indicated that the two different kinds of dot samples are largely divergent in their photo-induced antibacterial functions. In this work, three representative carbonization-produced samples from the precursor of citric acid–oligomeric polyethylenimine mixture with processing conditions of 200 °C for 3 h (CS200), 330 °C for 6 h (CS330), and microwave heating (CSMT) were compared with the classically synthesized CDots on their photo-induced antiviral activities. The results suggest major divergences in the activities between the different samples. Interestingly, CSMT also exhibited significant differences between antibacterial and antiviral activities. The mechanistic origins of the divergences were explored, with the results of different antimicrobial activities among the hybrid samples rationalized in terms of the degree of carbonization in the sample production and the different sample structural and morphological characteristics.more » « less
An official website of the United States government

